Ultrafast dynamics of heat flow across molecules

An ultrafast flash thermal conductance apparatus is used to study heat flow through aliphatic and aromatic molecules arranged in self-assembled monolayers (SAMs). The apparatus consists of a thin metal film which can be flash-heated by many hundreds of degrees in 1 ps using a femtosecond pulse. Heat flow from the metal surface into the SAM molecules is detected using vibrational sum-frequency generation (SFG) spectroscopy. The SAMs studied were alkanethiolates (AT) ranging from C6 to C24, benzenethiolate (BT) and benzylmercaptide (BMT). SFG in the CH-stretch region selectively probes transitions of the terminal methyl groups of AT and the CH moiety at the 4-position of the phenyl ring of BT and BMT (opposite the thiolate-surface bond). The SFG signal is sensitive to temperature-jump induced thermal disorder of the SAM and also to vibrational frequency shifts induced by the changing intramolecular vibrational populations. The SFG probe functions as a thermometer, and this thermometer is 1.5 Å thick with a response time of 1 ps. In the AT chains, a study of the length dependence is used to determine the rate heat flows across the metal–SAM interface and the rate of heat flow through the AT chains. The interface thermal conductance is 220 GW m⁻² s⁻¹. The AT molecular conductance is 50 pW K⁻¹ or 0.3 eV s⁻¹ K⁻¹. Heat flow through the AT chains is ballistic with a velocity of 1 km/s. Heat flow into BMT is slower than in BT because BMT has one additional methylene linker group. The BT and BMT structures evidence a thermally-initiated surface rearrangement occurring in a few tens of picoseconds. These SAMs are strained and the phenyl rings cannot adopt the most stable staggered herringbone structure. After the T-jump, the SAM molecules have enough freedom to relax into more favorable configurations.     

Potential and Charge Distribution at Semiconductor-electrolyte Interfaces

The present article deals with the basic concepts of charge and potential distribution at semiconductor-electrolyte interfaces. The authors use examples to show how external polarization and the variation of the electrolyte composition can change the potential drop across the space-charge region in the semiconductor and in the Helmholtz double layer at the interface. The article also contains a detailed discussion of the effects exerted by surface properties and by injection of carries on the distribution of charge and potential.     

Surface and interfacial structure of epitaxial SrTiO3 thin films on (0 0 1) Si grown by molecular beam epitaxy

Effects of relaxation of interfacial misfit strain and non-stoichiometry on surface morphology and surface and interfacial structures of epitaxial SrTiO₃ (STO) thin films on (0 0 1) Si during initial growth by molecular beam epitaxy (MBE) were investigated. In situ reflection high-energy electron diffraction (RHEED) in combination with X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron spectrometry (XPS) and transmission electron microscopy (TEM) techniques were employed. Relaxation of the interfacial misfit strain between STO and Si as measured by in situ RHEED indicates initial growth is not pseudomorphic, and the interfacial misfit strain is relaxed during and immediately after the first monolayer (ML) deposition. The interfacial strain up to 15 ML results from thermal mismatch strain rather than lattice mismatch strain. Stoichiometry of STO affects not only surface morphology but interfacial structure. We have identified a nanoscale Sr₄Ti₃O₁₀ second phase at the STO/Si interface in a Sr-rich film.     

Self-assembly of synthetic glycolipid/water systems

Glycolipids (amphiphiles that bear oligosaccharides as their hydrophilic headgroups) are of importance both scientifically and technically. This review describes recent advances in our understanding of the molecular correlations in phase behavior in aqueous glycolipids over the past several years. In the first part, we discuss how headgroup stereochemistry affects the phase behavior of glycolipids both in two- and three-dimensional systems. In the second part, we discuss the effects of alkyl chain structure and phase behavior of phytanyl-chained glycolipid/water systems. The physical properties of glycolipid/water systems depend strongly on the inter-headgroup interactions that are related to such factors as stereochemistry (conformation) and size of headgroups, type of sugar residues involved, alkyl chain structure, etc. Thus, apart from the conventional concept like ‘hydrophilic/lipophilic balance', explicit accounts of headgroup interactions are crucial to control the particular glycolipid/water system concerned. This is in marked contrast to the conventional amphiphile/water systems where the inter-headgroup interactions are in most cases simply repulsive.     

Effects of an impermeable wall in dissipative dynamics of saturated porous media

A phase transition model for porous media in consolidation is studied. The model is able to describe the phenomenon of fluid-segregation during the consolidation process, i.e., the coexistence of two phases differing on fluid content inside the porous medium under static load. Considering pure Darcy dissipation, the dynamics is described by a Cahn–Hilliard-like system of partial differential equations (PDE). The goal is to study the dynamics of the formation of stationary fluid-rich bubbles. The evolution of the strain and fluid density profiles of the porous medium is analysed in two physical situations: fluid free to flow through the boundaries of the medium and fluid flow prevented at one of the two boundaries. Moreover, an analytic result on the position of the interface between the two phases is provided.     

Investigation of metal–GaN and metal–AlGaN contacts by XPS depth profiles and by electrical measurements

Metal/GaN Schottky contacts have been studied by X-ray photoelectron spectroscopy (XPS). Au/GaN, Pt/GaN, Pd/GaN are sharp while Ti/GaN is diffuse with the following composition, starting from the surface: Ti+TiN, Ti+Ti_xGa_yN, Ti+Ti_xGa_yN+Ga, GaN+Ga. Au/AlGaN and Ni/AlGaN contacts are much broader than Au/GaN: Al and Ga are found more than 100 Å away from the interface. Schottky barrier height was measured for the Au/GaN, Pd/GaN, Pt/GaN, Au/AlGaN and Ni/AlGaN contacts.     

Estimation of surface energy and bonding between AlMgB14 and TiB2

Composites of AlMgB₁₄ with TiB₂ display a positive deviation from the rule-of-mixtures for hardness and wear resistance [1] (Ahmed et al., 2006). This suggests exceptionally strong bonding between the two boride phases. A contributing factor to the strong bonding may be a close matching of surface energy in the two phases. A calculation was performed to estimate the surface energy and its temperature dependence in AlMgB₁₄, based on the critical crack energy release rate and assuming covalent bonding. Results predict that the surface energy of the two phases differs by about 0.4 J/m². Similar results were found for other transition metal diborides, and the surface energy of AlMgB₁₄ was close to that of TiC and TiN, two materials commonly used as sintering aids for TiB₂.     

Thickness effects on the optical properties of layer-by-layer poly(p-phenylene vinylene) thin films and their use in energy-modulated structures

Poly(p-phenylene vinylene) (PPV) thin films were produced by layer-by-layer (LbL) method, using soluble PPV-precursor and dodecylbenzenesulfonate salt (DBS). The amount of deposited layers strongly influences the optical properties of the thermally converted PPV film. The absorbance and luminescence spectra of ultra-thin films (consisting of only two or three PPV layers) are shifted to smaller wavelengths with respect to spectra of thicker films. This is related to the smaller average conjugation length of polymer chains, resulting in a higher HOMO-LUMO gap energy of the material. However, if a thick film is produced by repeating the deposition process and thermal conversion of ultra-thin layers, the optical spectra are still displaced to higher energies in comparison with those of thicker films produced by the conventional continuous deposition of layers. This result enabled the production of multilayered polymeric films with modulated energy profile, taking the number of deposited layers as the only variable in the manufacturing process of the structure. The aim is to guide the excitation to specific regions of the material through the Förster-type energy transfer processes. Such systems can be used at interfaces electrode/polymer and/or electrode/polymeric active layers in order to improve the performance of organic optoelectronic devices.     

Wetting phase transitions and critical phenomena in condensed matter

Equilibrium wetting phase transitions and critical phenomena are discussed from a phenomenological point of view. The ubiquitous character of the wetting phase transition is illustrated through its occurrence in a variety of condensed matter systems, ranging from classical fluids to superconductors and Bose-Einstein condensates. The intriguing behaviour of the three-phase contact line and its line tension, at wetting, is an example of a fundamental problem in this field on which much progress has been made.